U.S. patent number 4,176,107 [Application Number 05/871,051] was granted by the patent office on 1979-11-27 for water-soluble dispersions of high molecular water-soluble polymers containing a surfactant and a water-soluble organic carrier which is a hydroxy compound containing repeating alkylene oxide units.
This patent grant is currently assigned to Buckman Laboratories, Inc.. Invention is credited to John D. Buckman, Wood E. Hunter, John D. Pera, Robert M. Taylor.
United States Patent |
4,176,107 |
Buckman , et al. |
November 27, 1979 |
Water-soluble dispersions of high molecular water-soluble polymers
containing a surfactant and a water-soluble organic carrier which
is a hydroxy compound containing repeating alkylene oxide units
Abstract
This invention is related to liquid polymer compositions and to
methods of preparing these compositions which comprise a high
molecular weight water-soluble vinyl addition polymer, water, one
or more surfactants, and a water-soluble polyalkylene glycol, or
water-soluble ethoxylated alcohol, alkylphenol or fatty acid.
Inventors: |
Buckman; John D. (Memphis,
TN), Hunter; Wood E. (Memphis, TN), Pera; John D.
(Memphis, TN), Taylor; Robert M. (Memphis, TN) |
Assignee: |
Buckman Laboratories, Inc.
(Memphis, TN)
|
Family
ID: |
25356618 |
Appl.
No.: |
05/871,051 |
Filed: |
January 20, 1978 |
Current U.S.
Class: |
524/317; 524/376;
523/332; 524/377 |
Current CPC
Class: |
D21H
17/34 (20130101); C08K 5/04 (20130101); C02F
1/5227 (20130101); C02F 1/54 (20130101); C08K
5/04 (20130101); C08L 57/00 (20130101) |
Current International
Class: |
C02F
1/52 (20060101); C02F 1/54 (20060101); D21H
17/34 (20060101); D21H 17/00 (20060101); C08K
5/00 (20060101); C08K 5/04 (20060101); C08L
033/02 () |
Field of
Search: |
;260/29.6E,29.6WQ |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Welsh; M. J.
Attorney, Agent or Firm: Trimble; Floyd
Claims
The invention having thus been described, what is claimed and
desired to be secured by Letters Patent is:
1. A composition comprising a water-soluble vinyl addition polymer,
water, at least one surfactant and a water-soluble organic carrier
selected from the group consisting of ##STR3## wherein R is
hydrogen or methyl; R.sup.1 is alkyl containing 6 to 26 carbon
atoms or alkyl substituted benzene in which the alkyl substituent
is branched or straight chain and contains 8 to 12 carbon atoms;
R.sup.2 is alkyl containing 5 to 17 carbon atoms; n varies from 2
to 20 and m varies from 3 to 10.
2. The composition of claim 1 wherein the water-soluble vinyl
addition polymer has units selected from the formulas A, B and C.
##STR4## wherein X is ##STR5## Y is phenyl, nitrile, carbomethoxy,
or carboethoxy and characterized in that all of the A units may
contain the same X or two or three different X groups and further
characterized in that M is alkali metal, alkaline earth metal, or
ammonium; R.sup.3 is hydrogen or methyl
R.sup.4 is alkylene containing 1 to 4 carbon atoms; R.sup.5 is
lower alkyl containing 1 to 4 carbon atoms; Z is an anion, and with
the proviso that unit B is present only in combination with unit A
and in minor amounts.
3. The composition of claim 1 wherein the surfactant is selected
from the group of nonionic, anionic, and cationic surfactants.
4. The composition of claim 1 wherein the water-soluble vinyl
addition polymer has a repeating unit of the formula ##STR6##
5. The composition of claim 1 wherein the water-soluble vinyl
addition polymer has a repeating unit of the formula ##STR7##
6. The composition of claim 1 wherein the water-soluble vinyl
addition polymer contains the units of the formula ##STR8##
7. The composition of claim 1 wherein the water-soluble vinyl
addition polymer contains the units of the formula ##STR9##
8. The composition of claim 1 wherein the water-soluble vinyl
addition polymer contains the units of the formula ##STR10##
9. The composition of claim 1 wherein the water-soluble organic
carrier is polyethylene glycol with a molecular weight of from 200
to 700.
10. The composition of claim 1 wherein the water-soluble vinyl
addition polymer contains the unit ##STR11## the surfactants are
sodium lauryl sulfate and phosphorylated ethylene oxide adduct of
an alkylphenol, and the water-soluble organic carrier is
polyethylene glycol having a molecular weight of about 400.
11. The composition of claim 1 wherein the water-soluble vinyl
addition polymer contains the units ##STR12## the surfactants are
sodium lauryl sulfate or alkyltrimethylammonium halide and
phosphorylated ethylene oxide adduct of an alkylphenol, and the
water-soluble organic carrier is polyethylene glycol having a
molecular weight of about 400.
12. The composition of claim 1 wherein the water-soluble vinyl
addition polymer contains the units ##STR13## the surfactants are
sodium lauryl sulfate and a phosphorylated ethylene oxide adduct of
an alkylphenol, and the water-soluble organic carrier is
polyethylene glycol having a molecular weight of about 400.
13. The method of preparing the liquid polymeric composition of
claim 1 wherein a water-soluble vinyl addition polymer is formed as
a water-in-oil suspension or emulsion in an inert hydrophobic
organic liquid containing at least one surfactant and
subsequently
a. separating the aqueous polymer phase from the oil phase and
mixing the said aqueous polymer phase with water, at least one
surfactant and a water-soluble organic carrier; or
b. mixing the water-in-oil suspension or emulsion with at least one
surfactant and a water-soluble organic carrier and removing the
inert hydrophobic organic liquid by distillation
wherein the said water-soluble organic carrier is selected from the
group consisting of ##STR14## wherein R is hydrogen or methyl;
R.sup.1 is alkyl containing 6 to 26 carbon atoms or alkyl
substituted benzene in which the alkyl substituent is branched or
straight chain and contains 8 to 12 carbon atoms; R.sup.2 is alkyl
containing 5 to 17 carbon atoms; n varies from 2 to 20 and m varies
from 3 to 10.
14. The method for preparing the liquid polymeric composition of
claim 13 wherein the water-soluble vinyl addition polymer has a
repeating unit of the formula ##STR15##
15. The method for preparing the liquid polymeric composition of
claim 13 wherein the water-soluble vinyl addition polymer contains
the units of the formula ##STR16##
16. The method for preparing the liquid polymeric composition of
claim 13 wherein the water-soluble vinyl addition polymer contains
the units of the formula ##STR17##
17. The method for preparing the liquid polymeric composition of
claim 13 wherein the water-soluble vinyl addition polymer has a
repeating unit of the formula ##STR18## the surfactants are sodium
lauryl sulfate and a phosphorylated ethylene oxide adduct of an
alkylphenol, and the water-soluble organic carrier is polyethylene
glycol having a molecular weight of about 200 to about 700.
18. The method for preparing the liquid polymeric composition of
claim 13 wherein the water-soluble vinyl addition polymer contains
the units ##STR19## the surfactants are sodium lauryl sulfate or
alkyltrimethylammonium halide and phosphorylated ethylene oxide
adduct of an alkylphenol and the water-soluble organic carrier is
polyethylene glycol having a molecular weight of about 200 to about
700.
19. The method for preparing the liquid polymeric composition of
claim 13 wherein the water-soluble vinyl addition polymer contains
the units ##STR20## the surfactants are sodium lauryl sulfate and a
phosphorylated ethylene oxide adduct of an alkylphenol and the
water-soluble organic carrier is polyethylene glycol having a
molecular weight of about 200 to about 700.
Description
BACKGROUND
Interest in the preparation and use of water-soluble polymers has
increased dramatically in recent years because of regulations
relating to pollution abatement. Various synthetic and natural
water-soluble polymers exhibit superior activity in waste water
clarification, flocculation, sludge dewatering, paper retention and
drainage, and in petroleum recovery operations. These high
molecular weight water-soluble polymers are available in three
forms, namely, as solids, as dilute aqueous solutions, and as
water-in-oil emulsions. High molecular weight solid water-soluble
polymers are usually difficult to dissolve despite the high
solubility in water. When added to water, the solid particles swell
and the exterior portions of the particles become covered with a
gelatinous water-polymer mixture which retards the movement of
water into the particle. As a result, excessive times are required
to achieve complete solubility, or else substantial loss in
effectiveness in an application area will result from the
incompletely dissolved polymer. To alleviate this problem, recent
improvements in the art have involved the development of more
rapidly dissolving water-in-oil emulsions of polyelectrolytes.
However, these materials are difficult to handle, and tend to
separate in the form of a polymer-poor oil phase and a polymer-rich
phase. They contain hydrocarbon oils which are flammable, foul
application equipment and result in cloudy solutions of
slow-dissolving polymer when added to water.
Accordingly it is an object of the present invention to provide a
liquid polymer composition which comprises a high molecular weight
water-soluble vinyl addition polymer, water, one or more
surfactants, and a water-soluble polyalkylene glycol, or
water-soluble ethoxylated alcohol, alkylphenol, or fatty acid.
It is a further object to provide a method for preparing high
solids dispersions of high molecular weight water-soluble polymers
in a water-soluble medium.
It is a further object to provide a composition which is composed
of a stable, easily handled liquid water-soluble polymer dispersion
in a water-soluble medium which is non-flammable, non-toxic, which
is storage-stable, and which furnishes a rapidly dissolving polymer
when added to water, resulting in clear solutions.
In brief, the foregoing objects and advantages are attained by use
of the new compositions of matter produced by forming a
water-soluble vinyl addition polymer as a water-in-oil suspension
or emulsion in an inert hydrophobic organic liquid containing at
least one surfactant and subsequently
a. separating the aqueous polymer phase from the oil phase and
mixing the said aqueous polymer phase with water, at least one
surfactant, and a water-soluble organic carrier, or
b. mixing the water-in-oil suspension or emulsion with at least one
surfactant and a water-soluble organic carrier and removing the
inert hydrophobic organic liquid by distillation.
The nature of the invention will become more apparent to those
skilled in the art by the preferred embodiments and description of
the invention which follows.
The Water-Soluble Polymer
The principal ingredient of this invention is the water-soluble
vinyl addition polymer having units selected from the formulas A,
B, and C. ##STR1## Y is phenyl, nitrile, carbomethoxy, or
carboethoxy and characterized in that all of the A units may
contain the same X or two or three different X groups and further
characterized in that M is alkali metal, alkaline earth metal, or
ammonium; R.sup.3 is hydrogen or methyl;
R.sup.4 is alkylene containing 1 to 4 carbon atoms; R.sup.5 is
lower alkyl containing 1 to 4 carbon atoms; Z is an anion, and with
the proviso that unit B is present only in combination with unit A
and in minor amounts.
Such materials are well known to those skilled in the art and
include either solid materials or the aqueous polymer phase which
results from heterogeneous polymerizations wherein an aqueous phase
is dispersed in a water-insoluble organic phase. These are
frequently referred to as water-in-oil polymerizations and this
terminology will be used in the following text. Such polymers may
be non-ionic, cationic, anionic, or amphoteric, depending upon the
nature of the ethylenically unsaturated monomers which are used in
their preparation.
Non-ionic, water-soluble, vinyl addition polymers result from the
polymerization of acrylamide or methacrylamide. They also result
from copolymerization of acrylamide or methacrylamide with other
ethylenically unsaturated monomers, such as acrylonitrile, styrene,
acrylate or methacrylate esters, and the like, in such proportions
that the resultant polymer is water-soluble.
Anionic polymers result from the polymerization of acrylic acid or
its salts, methacrylic acid or its salts, vinylbenzylsulfonic acid
or its salts, 2-acrylamido-2-methylpropane sulfonic acid or its
salts, or 2-sulfoethylmethacrylate or its salts, and the like.
Included in this category of anionics are copolymers of the above
described anionic monomers with the non-ionic monomers, acrylamide,
methacrylamide, etc.
Cationic polymers are formed from dimethylaminoalkylacrylates and
methacrylates and their quaternary derivatives,
dimethylaminopropylmethacrylamides and quaternary derivatives,
diallyldimethylammonium halides, and vinylbenzyltrialkylammonium
chlorides. Similarly, copolymers of these cationic monomers with
the non-ionic monomers, acrylamide, methacrylamide, etc., are
included.
Included in the above definition of anionic and cationic polymers
are the reaction products of non-ionic polymers with chemical
reagents to furnish anionic or cationic functionality. For example,
anionic functionality can be produced by hydrolysis of
polyacrylamide to various degrees of acrylate content, while
reaction with formaldehyde and bisulfite provides sulfonate
functionality. Alternately, polyacrylamide can be reacted with
hypochlorite or hypobromite by the Hoffmann reaction to give amine
functionality, or reacted with formaldehyde and a dialkylamine to
furnish the Mannich amine derivative. Such amines can be alkylated
to form the quaternaries.
Polyampholytes contain both cationic and anionic functionality in
the same polymer molecule. Such molecules can be formed by
copolymerization of anionic monomers such as those listed above,
with cationic monomers such as those described above. Alternately,
an anionic or cationic polyelectrolyte can be chemically modified
to provide the polyampholyte. For example, a copolymer of
acrylamide and sodium acrylate can be reacted with formaldehyde and
dialkylamine to furnish a polyampholyte containing acrylate with
amine functionality.
Included in the definition of the water-soluble polymer of this
invention are the products of solution polymerization and
water-in-oil heterogeneous polymerization. It is essential to our
invention that the polyelectrolyte be in the form of an aqueous
polymer phase, preferably, as the polymer-water phase resulting
from heterogeneous water-in-oil polymerization. Both the inverse
suspension polymerization method of Friedrich, et. al. (U.S. Pat.
No. 2,982,749), and the inverse emulsion polymerization methods of
Vanderhoff, et. al. (U.S. Pat. No. 3,284,393) and Anderson, et. al.
(U.S. Pat. No. 3,826,771), are included in this latter category.
Particularly preferred is the polymer-water phase which results
from suspension polymerization of a water-soluble vinyl monomer
dispersed in a water-insoluble organic phase.
The Dispersion Medium
For purposes of our invention, the water-soluble liquid into which
the polymer is dispersed is termed the carrier. Suitable carriers
for the successful formation of stable dispersions include certain
water-soluble liquids which possess a suitable combination of
hydrophobic groups and hydrophilic groups, such that the aqueous
polyelectrolyte can be suitably dispersed therein, without
precipitation, dewatering, or solubilizing the polyelectrolyte.
These carriers may be selected from the group consisting of
##STR2## wherein R is hydrogen or methyl; R.sup.1 is alkyl
containing 6 to 26 carbon atoms or alkyl substituted benzene in
which the alkyl substituent is branched or straight chain and
contains 8 to 12 carbon atoms; R.sup.3 is alkyl containing 5 to 17
carbon atoms; n varies from 2 to 20 and m varies from 3 to 10. We
have found particularly effective carriers to be polyalkylene
glycols such as polyethylene glycol of molecular weight equal to
200 to 600, polypropylene glycol of molecular weight equal to 150
to 1000, ethoxylated derivatives of linear alcohols, in which the
ethylene oxide content ranges from three moles to seven moles,
ethoxylated derivatives of alkylphenols, in which the ethylene
oxide content ranges from three to ten moles, and ethoxylated
derivatives of fatty acids and their derivatives which contain
enough ethylene oxide to render them water-soluble.
For economic purposes, these carriers may be diluted with
co-solvents which furnish water-compatible combinations. Examples
of such diluents include alcohols, such as 2-ethylhexanol,
2-octanol, and 1-hydroxyalkanes, tri- and tetraethylene glycols,
ethers such as the methyl, ethyl, isopropyl, or butyl ethers of
glycols, ketones such as diacetone alcohol, amides such as
dimethylformamide, or esters such as methoxyethyl acetate.
The Surface-Active Agent
It is an essential part of the instant invention to use suitable
surface-active agents in order to disperse the aqueous
water-soluble vinyl addition polymer into the water soluble
dispersion medium. Those materials which have been found most
effective include non-ionic, cationic, and anionic types. Examples
of non-ionic surface-active agents which are suitable include
ethylene oxide adducts of linear alcohols and alkylphenols,
sorbitan esters such as sorbitan monooleate, sorbitan monostearate,
and sorbitan monopalmitate, ethoxylated sorbitan esters such as the
5-20 mole ethylene oxide adducts of sorbitan monooleate, sorbitan
tristearate, or sorbitan monostearate, fatty acid esters of
polyalkylene oxides such as polyethylene glycol 200 to 600
monooleate, monostearate, dioleate, or monopalmitate, and
ethoxylated fatty amides such as the ethylene oxide adducts of tall
oil fatty acid amide, and the like.
Examples of cationic surface-active agents include salts of long
chain quaternary amines such as cetyltrimethylammonium bromide,
hexadecyltrimethylammonium chloride, and octadecyltrimethylammonium
chloride. Also useful are oxazoline esters of long chain fatty
acids such as the oleyl ester, tall oil ester, or caprylic acid
ester of oxazolines prepared from tris(hydroxymethyl)amino methane,
or 2-amino-2-ethyl-1,3-propanediol. Cationic surfactants which are
copolymers of olefins with N-vinylpyrrolidone also are useful.
Examples of anionic surfactants include salts of alkyl sulfates and
sulfonates, such as sodium lauryl sulfate, sodium cetyl sulfonate,
potassium stearyl sulfonate, or potassium stearyl sulfate, and
phosphate esters of ethoxylated linear alcohols and
alkylphenols.
Although some of the beneficial aspects of this invention can be
obtained with one surfactant alone, it has been found that
combinations of surfactants provide more efficient overall results.
In particular, the use of phosphorylated derivatives of ethoxylated
nonyl phenols in combination with sodium lauryl sulfate or
alkyltrimethylammonium halides gives fluid dispersions with long
term stability.
Having described the essential constituents of the liquid polymeric
composition which forms the basis of our invention, a more detailed
description of the process for forming the polymer dispersion can
be set forth.
Formation of the Dispersion
In order to successfully form the dispersion of the instant
invention, it is preferable to use water-swollen polymer particles.
This requirement is most easily accomplished by conducting a
heterogeneous water-in-oil polymerization. The water phase
containing the water-swollen polymer phase is recovered from the
water-oil mixture by mechanical means such as separation or
distillation. Conversely, a similar polymer-water paste would
result from mechanical mixing of solid polymer and water. Smooth
dispersion into the carrier necessitates the use of surface active
agents as components of the water-swollen polymer phase. The
surface active agent of this aspect of the invention is composed of
low HLB materials which are well documented in the literature.
Particularly effective are sorbitan esters and their ethoxylated
derivatives. These surface active agents are used in amounts of 1
percent to 20 percent based on the water-polymer composition.
Preferred amounts of water and polymer in the aqueous polymer phase
range from 20 percent to 70 percent polymer and from 80 percent to
30 percent water. Percent as used throughout the specification is
by weight.
In order to form the dispersion, this water-polymer phase that is
stabilized with low HLB surfactant is added to a mixture of
carrier, water, and dispersants, or vice-versa. This mixture or
carrier phase is composed of water in the amount of 0 to 30
percent, carrier in the amount of 99.5 percent to 69.5 percent, and
dispersants in the amount of 0.5 percent to 30.5 percent. The
dispersant may be sodium lauryl sulfate or quaternary alkylamine
halide and phosphate ester in the ratio of 1:10 to 10:1. After
addition of the water-polymer phase to the carrier phase, or
vice-versa, the dispersion is mixed to provide the desired
fluidity. Agitation can range from mechanical agitation as provided
by ordinary laboratory mixers, to homogenization, as provided by
blenders, ball mills, etc.
In order to prepare the aqueous polymer phase by water-in-oil
heterogeneous polymerization, any of the techniques described in
the patents cited above may be used. We particularly prefer the use
of the inverse suspension polymerization procedure as outlined in
U.S. Pat. No. 2,982,749, utilizing suspending agents such as
sorbitan esters and their ethoxylated derivatives. However, similar
results are obtained when using inverse emulsion polymerization, as
in Vanderhoff, or the latex polymerization procedure, as in
Anderson, et. al. At completion of polymerization, the oil phase is
removed by centrifugation, decantation, or distillation. This
provides an aqueous-polymer phase as specified above. By conducting
the inverse polymerization with an aqueous monomer concentration of
20 percent to 70 percent, the resultant polymer-water phase will be
of the required composition for dispersion into the carrier as
outlined above; alternately, the polymerization can be carried out
at low monomer concentrations, followed by azeotropic water removal
to provide the desired polymer-water phase. Once the polymer-water
phase is separated by any conventional means, the formulation into
the polymeric dispersion of the instant invention can be conducted
as defined above.
As an alternate to the isolation or preparation of an aqueous
polymer phase, the preparation of the polymeric dispersion can be
conducted in one step from the water-in-oil polymer system. This
approach involves addition of the carrier phase to the water-in-oil
polymer suspension or emulsion. Distillation of the water-insoluble
organic phase furnishes the polymeric dispersion.
Dissolving the Dispersion
The dispersion of our invention can be dissolved in water by
addition of the dispersion to the water under suitable agitation.
Complete solubility results. In some cases, the rate of
solubilization of the dispersion can be increased by the addition
of suitable surface active agents to the water, but this is not
essential to the successful operation of our invention. If the use
of surfactants is desired, ethoxylated linear alcohols or
ethoxylated alkyl phenols can be used.
Uses
The polymers of this invention are useful in the pulp and paper
industry, for treatment of municipal and industrial water and
effluents, in the pretroleum industry in both drilling and
production, in mineral processing, and other industries.
In the paper industry, the non-ionic, cationic and anionic
water-soluble polymers may be used as drainage and retention aids.
Lower molecular weight polymers and copolymers are useful as dry
strength resins. Both anionic and cationic polymers may be used as
retention aids but the cationic polymers are generally more useful
in this area. Other uses in the paper industry include
clarification of white water, as wet strength resins, and as
creping aids.
Water treatment uses for both industry and municipal supplies
include clarification, phosphate removal, boiler water treatment,
and sludge dewatering. Municipal and industrial waste water
processors may utilize these polymers for primary flocculation,
sludge thickening and dewatering, elutriation, and phosphate
removal. The flocculation, phospate removal, boiler water treatment
and influent process water usually utilize anionic polymers.
Cationics are used mainly in sludge handling operations in plants
with activated sludge secondary treatment facilities.
The water-soluble polymers of this invention can be used in mineral
processing to remove clay, and other fine waste particles from
extracting liquors and wash water which must be recycled. These
types of uses apply to processes involving copper, coal, potash,
uranium, titanium dioxide, calcium carbonate, iron, zinc, gold,
silver, lead, rare earth metals, feldspar, mica and quartz. The
polymers are particularly useful as flocculants for clarifying
waste waters at phosphate, bauxite, and barite mines.
In the petroleum industry, the water-soluble polymers of this
invention can be used to lower the pumping friction, to raise the
low shear viscosity to control fluid loss to the surrounding
strata, and to push the oil to the pumping well. The polymers are
also used in drilling muds, completion and work-over fluids,
acidizing and fracturing fluids, in barrier fluids to control the
water-oil ratio and in polymer flooding operations. The use of
these polymers in flooding operations is becoming more important as
the price of petroleum continues to increase and the availability
continues to decrease. The use of these polymers behind a micellar
fluid allows the petroleum producer to obtain a third crop of oil
from the fields.
Other uses for the polymers of this invention include those where
the products are utilized as thickeners and suspending agents in
aqueous emulsions, such as water-thinned paints. Still other uses
include hair sprays, gelatin substitutes for photographic
applications, components of adhesives and explosive formulations,
binders for sand, ores, and coal.
In order to disclose the nature of the present invention still more
clearly, the following illustrative examples will be given. It is
to be understood, however, that the invention is not to be limited
to the specific conditions or details set forth in these examples
except insofar as such limitations are specified in the appended
claims.
EXAMPLE 1
Formation of Aqueous Polymer Phase
To a one-liter round bottom flask, equipped with mechanical
agitator, thermometer, condenser, and nitrogen sparge tube, is
added 400 g. of heptane, 7.5 g. sorbitan monooleate, and 5.5 g. of
a 20 mole ethylene oxide adduct of sorbitan tristearate. With
agitation of 400-1200 rpm., the monomer phase consisting of 155.1
g. acrylamide, 155.1 g. deionized water, and 0.02 g.
ethylenediamine tetraacetic acid tetrasodium salt chelant is added.
The suspension is heated to the reaction temperature of 45.degree.
C. under nitrogen purge, whereupon the addition of 0.04 g. of
ammonium persulfate causes initiation of polymerization within 10
minutes. After the polymerization is complete (usually 3-4 hrs.),
the heptane is removed from centrifugation to furnish 324 g. of
white polymeric paste.
EXAMPLE 2
Formation of the Dispersion
To 16.0 g. of polymer paste of Example 1 is added a mixture of 6.0
g. of polyethylene glycol 400, 1.0 g. water, 0.1 g. of sodium
lauryl sulfate, and 0.1 g. of phosphorylated ethylene oxide adduct
of an alkylphenol. The mass is mixed well with a spatula to furnish
a fluid, milky-white dispersion. Storage of the dispersion for one
week in an oven at 50.degree. C. resulted in no separation of
phases. The dispersion (5.7 g.) was added to 200 g. of water under
mechanical agitation to give a 1 percent polymer solution, which
had a Brookfield viscosity of 1650 cps. and an intrinsic viscosity
of 18.0 dl./g. Polyacrylamides with this intrinsic viscosity
generally have a molecular weight of about five million.
EXAMPLE 3
The procedure of Example 2 was repeated except that the
surfactants, sodium lauryl sulfate and the phosphorylated ethylene
oxide adduct of an alkylphenol were replaced by the surfactants
included in Table 1.
Table 1 ______________________________________ Dispersants for
aqueous nonionic polymer phase Run No. Surfactants Dispersion
Appearance ______________________________________ 1 ethoxylated
sorbitan oleate/oleyl alcohol smooth paste-like fluid 2 ethoxylated
dodecylphenol dewatered 3 xanthan gum smooth, fluid liquid 4
ethoxylated fatty acid smooth, fluid 5 phosphorylated ethoxylate
smooth, fluid ______________________________________
EXAMPLE 4
The procedure of Example 2 was repeated except that the
polyethylene glycol 400 was replaced by the water-soluble organic
substances included in Table 2.
Table 2 ______________________________________ Water-soluble
organic carriers used in the dispersions Run No. Carrier Dispersion
Appearance ______________________________________ 1 polyethylene
glycol 300 smooth, fluid liquid 2 ethoxylated linear alcohol
smooth, fluid liquid 3 diacetone alcohol fluid, paste-like liquid 4
polypropylene glycol 400 thick, paste-like fluid
______________________________________
EXAMPLE 5
The procedure of Example 2 was repeated except that the organic
substance used was an ethoxylated linear alcohol which was mixed
with various organic diluents. The results are included in Table
3.
Table 3 ______________________________________ Effect of diluents
Carrier Run No. Diluent Percent Dispersion Appearance
______________________________________ 1 2-ethylhexanol 17-33
smooth, fluid liquid 2 1-decanol 33-50 fluid, liquid 3 2-octanol
17-33 smooth dispersion 4 diacetone alcohol 50 paste-like fluid 5
dimethyl 25 smooth, fluid liquid formamide
______________________________________
EXAMPLE 6
The procedure of Example 1 was repeated using a monomer phase
consisting of 155.1 g. acrylamide, 155.1 g. deionized water, 13.3
g. of acrylic acid, 0.03 g. of ethylenediamine tetraacetic acid
tetrasodium salt, and 15.5 g. of 50 percent sodium hydroxide to a
monomer solution pH of 7.0. After completion of the polymerization,
the polymer phase was isolated by centrifugation. Blending 13.0 g.
of paste with a solution of 1.0 g. water, 0.2 g. sodium lauryl
sulfate, 0.2 g. of the phosphorylated ethylene oxide adduct of an
alkylphenol, and 6.0 g. polyethylene glycol 400 afforded a fluid,
milky dispersion of polymer. This dispersion remained stable after
4 weeks at room temperature. A 0.25 percent aqueous solution of the
polymer had a Brookfield viscosity of 500 centipoise and an
intrinsic viscosity of 13.7 dl./g., which is usually indicative of
a molecular weight of about eight million.
EXAMPLE 7
The procedure of Example 6 was repeated using different surfactants
and the results are included in Table 4.
Table 4 ______________________________________ Dispersants for
aqueous anionic polymer phase Run No. Surfactants Dispersion
Appearance ______________________________________ 1 ethoxylated
sorbitan oleate smooth, viscous liquid 2 ethoxylated tall oil
smooth, paste-like liquid 3 ethoxylated linear alcohol smooth,
fluid liquid 4 phosphorylated linear smooth, fluid liquid alcohol 5
sodium xylene sulfonate dewatered 6 xanthan gum smooth, viscous
liquid 7 oleyl alcohol dewatered 8 cetyltrimethylammonium smooth,
fluid liquid bromide ______________________________________
EXAMPLE 8
Preparation of Cationic Polymer Dispersion
The experiment of Example 1 was repeated using a monomer phase
composed of 150.0 g. acrylamide, 150.0 g. deionized water, and 28.0
g. of 80 percent dimethylaminoethylmethacrylate dimethyl sulfate.
After polymerization, the suspension was treated with a mixture of
97.9 g. polyethylene glycol 400, 17.0 g. water, 1.7 g.
cetyltrimethylammonium bromide, and 3.2 g. of the phosphorylated
ethylene oxide adduct of an alkylphenol. After thorough mixing, the
heptane was removed at 46.degree. C. under vacuum. The result was a
fluid, milky dispersion of cationic polymer. The Brookfield
viscosity of a 1 percent solution of the polymer was 2650
centipoise which is usually indicative of a molecular weight of
about two to four million.
EXAMPLE 9
The procedure of Example 8 was repeated using different surfactants
and the results are included in Table 5.
Table 5 ______________________________________ Dispersants for
aqueous cationic polymer phase Dispersion Run No. Surfactant
Appearance ______________________________________ 1
cetyltrimethylammonium fluid, smooth liquid bromide 2
hexadecyltrimethylammonium fluid, smooth liquid chloride 3
octadecyltrimethylammonium fluid, smooth liquid chloride 4
olefin-N-vinylpyrrolidone fluid, smooth liquid copolymer
______________________________________
EXAMPLE 10
Preparation of a Liquid Polymer from Hydrolyzed Polyacrylamide
The hydrolyzed polyacrylamide was prepared according to Example 4
of U.S. Pat. No. 3,998,777 as a water-in-oil emulsion. The oil was
separated by centrifugation to leave a slightly yellow polymer
paste (calculated polymer concentration in the paste of 40.4
percent), and 18.0 grams of the paste was mixed with a solution of
1.2 g. phosphorylated ethylene oxide adduct of an alkyl phenol, and
6.0 g. polyethylene glycol 400. The resultant liquid was smooth and
fluid, and completely miscible with water.
EXAMPLE 11
Preparation of a Liquid Polymer from Manniched Polyacrylamide
The Mannich derivative of polyacrylamide was prepared according to
Example 5 of U.S. Pat. No. 4,013,606 as a water-in-oil emulsion.
The oil was separated to leave a white paste and 16.0 g. of this
paste was mixed with a solution of 0.6 g. phosphorylated ethylene
oxide adduct of an alkylphenol, and 6.0 g. polyethylene glycol 400.
The resultant liquid was fluid and smooth.
EXAMPLE 12
The polymeric compositions described in Examples 2, 6 and 8 were
tested for their effectiveness in the retention of titanium dioxide
pigment in a pulp pad following the method described in Example 18
of U.S. Pat. No. 4,054,542, which disclosure is hereby made a part
of this application. The percent improvement in retention was
calculated using the following formula: ##EQU1## The increase in
retention was significant in every case, and increases were better
or equal to those obtained with commercial retention aids in most
instances. The results are tabulated in Table 6.
Table 6 ______________________________________ Improvement in
retention of titanium dioxide Use Rate Improvement Pound per ton in
Retention Polymer Dispersion Test of pulp Percent
______________________________________ From Example 2 A 0.5 2.8 A
0.75 6.0 B 1.0 19.0 From Example 6 A 0.5 20.0 B 1.0 13.9 From
Example 8 A 0.5 17.8 B 1.0 19.0
______________________________________ Test A pH of pulpTiO.sub. 2
slurry was 7 Test B pH of pulpTiO.sub.2 slurry was adjusted to pH
4.7 with alum
EXAMPLE 13
The polymeric compositions described in Examples 2, 6 and 8 were
tested as flocculants using a mixture of pulp and clay. The
procedure used is the one described in Example 19 of U.S. Pat. No.
4,054,542, which disclosure is hereby made a part of this
application. The flocculating properties of all of the polymers
were significant and the results were better or equivalent in most
cases to those obtained with commercial flocculating agents.
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